Supporting Information. Orientation Direction Control in Liquid Crystalline Photoalignable Polymeric Films by Adjusting the Free-Surface Condition

Transcription

1 Supporting Information Orientation Direction Control in Liquid Crystalline Photoalignable Polymeric Films by Adjusting the Free-Surface Condition Kazutoshi Miyake a, Hiromi Ikoma a, Makoto Okada b, Shinji Matsui b, Mizuho Kondo a, Nobuhiro Kawatsuki a * a Department of Applied Chemistry, Graduate School of Engineering, University of Hyogo, 267 Shosha, Himeji, Hyogo , Japan b Laboratory of Advanced Science and Technology for Industry, University of Hyogo, 3--2 Koto, Kamigori, Ako, Hyogo Japan. Experimental.. Film preparation and photoreaction. Thin LCP films (approximately.2-µm thick) were prepared by spin-coating a methylene chloride solution of polymers (2. w/w%) onto quartz or CaF 2 substrates. A high-pressure Hg lamp equipped with a glass plate placed at Brewster s angle and a 365-nm band-pass filter (Asahi Spectra REX-25) were used for the photoreactions. The light intensity at 365 nm was 3 mw/cm Characterization. H-NMR spectra using a Bruker DRX-5 FT-NMR and FT-IR spectra (JASCO FTIR-4) confirmed the polymer. The molecular weights of the polymers were measured by GPC (Tosoh HLC-82 GPC system with a Tosoh TSKgel column using chloroform as the eluent) calibrated using polystyrene standards. The thermal properties were examined using a polarization optical microscope (POM; Olympus BX5) equipped with a Linkam TH6PM heating and cooling stage as well as differential scanning calorimetry (DSC; Seiko-I SSC52H). The polarized absorption UV vis and FT-IR spectra were measured with a Hitachi U-3 spectrometer equipped with Glan Taylor polarization prisms and an FTIR-4 system, respectively. As a measure of the photoinduced optical anisotropy, the photoinduced in-plane dichroic ratio (DR) was evaluated using the polarization absorption spectra, which is estimated as DR = A A A + A, ()

2 where A and A are the absorbances parallel and perpendicular to polarization (E) of LP 365-nm light, respectively. The surface topology was evaluated using atomic force microscopy (AFM; E-sweep/NanoNavi, Hitachi High-Tech Science Co., tapping mode for 5 5 µm 2 are and an optical surface profiler (VertScan2. R33, Ryoka Systems Inc., µm 2 or µm 2 are..3. Inkjet printing. Top coating of AN molecules on PNBAM films was performed using an inkjet apparatus (LabJet-, MICROJET Co. Ltd) from AN/ethylene glycol solution (2 wt/vol-%) at 3 C. After printing AN, the films were annealed at C for 2 min. 2. Supporting Figures C-H - MB Wavenumber (cm - ) 5 c) (AN-coated) d).4.2 +AN Wavenumber (cm - ) 5 Figure S. Changes in ( the UV vis absorption and ( the FT-IR spectra of the PMBM film before and after annealing at C. Changes in (c) the UV vis absorption and (d) the FT-IR spectra of the as-coated and AN-coated PMBM film before and after annealing at C. Black (red) line is the absorption spectrum of the as-coated (annealed) film, while the blue line is the differential spectrum before and after annealing. Green lines in (d) is the absorption after coating with AN.

3 Absorbance (a.u. at 282 nm) G LC Isotropic Absorbance (a.u. at 265 nm) Temperature ( C).2 Figure S2. Changes in the absorbance ( at 282 nm of PNBAM and ( at 265 nm of the PMBM films annealed at various temperatures for 2 min C LC Isotoropic Temperature ( C) Absorbance at 282 nm (a.u.) Absorbance at 282 nm (a.u.) c) Figure S3. (a, Angular dependences of the absorbance at 282 (265) nm of the PNBAM (PMBM) film before and after annealing at () C for 2 min. (c,d) Angular dependences of the absorbance at 282 (265) nm of the AN-coated PNBAM (PMBM) film before and after annealing at () C for 2 min. Absorbance at 265 nm (a.u.) Absorbance at 265 nm (a.u.) d)

4 c) 3 µm Figure S4. POM photographs of the PNBAM films under crossed polarizers. film ( before and ( after annealing at C. (c) AN-coated film annealed at C. +NA NA Wavenumber (cm ) Figure S5. Changes in ( the UV vis absorption and ( the FT-IR spectra of an as-coated, NA-coated PNBAM film, and after annealing at C. Black (red) line is the absorption spectrum of a as-coated (annealed) film, while the blue line is the difference spectrum before and after annealing. Green line is the absorption after coating with NA.

5 at 5 C c) Absorbance at 282 nm (a.u.) annealed at 5 C Wavenumber (cm ) d) Figure S6. Change in ( the UV vis absorption and ( the FT-IR spectra of the as-coated PNBAM film and after annealing at 5 C. (c) Angular dependence of the absorbance at 282 nm for the PNBAM film before and after annealing at 5 C for 2 min. (d) POM photograph of the PNBAM film after annealing at 5 C. Figure S7. (a, Three-dimensitional images of the surface topologies (5 5 µm2, AFM tapping mode) and (c,d) the surface roughness (95 µm, VertScan) of PNBAM films. (a,c) NA-coated film after annealing at C and (b,d) the as-coated film after annealing at 5 C.

6 Figure S8. (a-d) Three-dimensional images of surface topologies (5 5 µm 2, AFM tapping mode) and (e-h) the surface roughness (95 µm, VertScan) of PMBM films. (a,e) film, (b,f) the as-coated film after annealing at C, (c,g) the AN-coated film after annealing at C, and (d,h) the as-coated film after annealing at 4 C,

7 Figure S9. Three-dimensional image of the surface topology ( µm 2, surface profiler) and the surface roughness (235 µm, surface profiler) of the boundary of the partly AN-coated PMBM film after annealing at C. Arrows indicate the AN-coated and the uncoated areas. Figure S. Schematic of unevenness formation at the boundary between the AN-coated and the uncoated areas of LCP films.

8 Exposed ( ) Exposed ( ) Figure S. Changes in the polarized UV vis absorption spectra of the NA-coated PNBAM film annealed at C, and after subsequent irradiation with LP 365-nm light for J/cm 2. Figure S2. POM photographs of (a, the AN-coated film after annealing at C, and (c,d) subsequent exposure to LP 365-nm light for J/cm 2. Arrows indicate the polarizer and analyzer directions.

9 Figure S3. POM photographs of after annealing the AN-patterned coated PNBAM films at C. (a, Inkjet-coated film. (c,d) Sublimation-coated film. White arrows indicate the polarizer and analyzer directions. Figure S4. POM photographs of a patterned PNBAM film. The AN molecules are coated by sublimation, and the film is subsequently annealed at C and exposed to LP 365-nm light for J/cm 2. White arrows indicate the polarizer and analyzer directions, and blue arrow is the in-plane orientation direction.